(Z)-2-Sulfanyl­idene-5-(thio­phen-2-yl­methyl­idene)imidazolidin-4-one

Asiri, A.M.; Faidallah, H.M.; Al-Youbi, A.O.; Sobahi, T.R.; Ng, S.W.

doi:10.1107/S1600536811033034

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2429

doi:10.1107/S1600536811033034

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(Z)-2-Sulfanylidene-5-(thiophen-2-ylmethylidene)imidazolidin-4-one

Abdullah M. Asiri,^a,^b Hassan M. Faidallah,^a Abdulrahman O. Al-Youbi,^a Tarik R. Sobahi ^a and Seik Weng Ng ^c,^a ^*

^aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia, ^bCenter of Excellence for Advanced Materials Research, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 13 August 2011; accepted 15 August 2011; online 27 August 2011)

The molecule of the title compound, C₈H₆N₂OS₂, has a V shape with two five-membered rings attached to a methylene C atom. All non-H atoms are approximately coplanar (r.m.s. deviation = 0.096 Å). In the crystal, molecules are linked by N—H⋯O hydrogen bonds into layers. The thiophene ring is disordered over two positions; the major orientation has an occupancy of 0.683 (3). is there an intramolecular N---H...S bond?

Related literature

For two 5-aryl-2-thioxoimidazolin-4-ones, see: Chowdhry et al. (2000 ); Książek et al. (2009 ).

Experimental

Crystal data

C₈H₆N₂OS₂
M_r = 210.27
Triclinic, $[P \overline 1]$
a = 6.1022 (6) Å
b = 7.0806 (8) Å
c = 11.0425 (13) Å
α = 72.582 (11)°
β = 76.116 (10)°
γ = 75.640 (9)°
V = 433.87 (8) Å³
Z = 2
Cu Kα radiation
μ = 5.22 mm⁻¹
T = 100 K
0.25 × 0.20 × 0.02 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.356, T_max = 0.903
2599 measured reflections
1677 independent reflections
1519 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.122
S = 1.04
1677 reflections
134 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.88	2.20	2.873 (2)	133
Symmetry code: (i) x+1, y, z.

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811033034/bt5612sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811033034/bt5612Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811033034/bt5612Isup3.cml

checkCIF report

Comment top

The crystal structures of only a small number of 5-aryl-2-thioxoimidazolidin-4-ones have been reported, with that of the phenyl homolog been described only recently. The bond dimensions of the parent compound are used to explain the nature of the products of its cycloaddition reaction (Książek et al., 2009). The 2-pyridyl derivative is also a flat molecule (Chowdhry et al., 2000) The thienyl analog (Scheme I) is similarly planar (r.m.s. deviation 0.096 Å). The molecule has a somewhat butterfly shape with the two five-membered rings attached to the methylene carbon (Fig. 1). The –NH– unit at the 4-position (of one ring) points towards the S atom in the 2-position (of the other ring); however, the interaction is too weak to lock the molecule so that the thienyl ring is able to adopt two orientations. Two molecules are linked by an N–H···O hydrogen bond across a center-of-inversion to form a dimer.

Related literature top

For two 5-aryl-2-thioxoimidazolin-4-ones, see: Chowdhry et al. (2000); Książek et al. (2009).

Experimental top

Thiophene-2-carboxaldehyde (1.10 g, 10 mmol) in ethanol (20 ml) was added to a solution of the 2-thiohydantoin (1.16 g,10 mmol) in 20% ethanolic potassium hydroxide (20 ml). The mixture was stirred for 6 h. The mixture was then poured into water (200 ml). The precipitate that separated when this was acidified with 10% hydrochloric acid was collected and recrystallized from ethanol.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Ansiotropic displacement ellipsoid plot (Barbour, 2001) of C₈H₆N₂OS₂ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The disorder in the thienyl ring is not shown.

(Z)-2-Sulfanylidene-5-(thiophen-2-ylmethylidene)imidazolidin-4-one top

Crystal data top

C₈H₆N₂OS₂	Z = 2
M_r = 210.27	F(000) = 216
Triclinic, P1	D_x = 1.610 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 6.1022 (6) Å	Cell parameters from 1386 reflections
b = 7.0806 (8) Å	θ = 4.3–73.9°
c = 11.0425 (13) Å	µ = 5.22 mm⁻¹
α = 72.582 (11)°	T = 100 K
β = 76.116 (10)°	Plate, yellow
γ = 75.640 (9)°	0.25 × 0.20 × 0.02 mm
V = 433.87 (8) Å³

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1677 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	1519 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.027
Detector resolution: 10.4041 pixels mm^-1	θ_max = 74.1°, θ_min = 4.3°
ω scans	h = −4→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −8→8
T_min = 0.356, T_max = 0.903	l = −11→13
2599 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0832P)² + 0.1141P] where P = (F_o² + 2F_c²)/3
1677 reflections	(Δ/σ)_max = 0.001
134 parameters	Δρ_max = 0.33 e Å⁻³
6 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₈H₆N₂OS₂	γ = 75.640 (9)°
M_r = 210.27	V = 433.87 (8) Å³
Triclinic, P1	Z = 2
a = 6.1022 (6) Å	Cu Kα radiation
b = 7.0806 (8) Å	µ = 5.22 mm⁻¹
c = 11.0425 (13) Å	T = 100 K
α = 72.582 (11)°	0.25 × 0.20 × 0.02 mm
β = 76.116 (10)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1677 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1519 reflections with I > 2σ(I)
T_min = 0.356, T_max = 0.903	R_int = 0.027
2599 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	6 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.04	Δρ_max = 0.33 e Å⁻³
1677 reflections	Δρ_min = −0.44 e Å⁻³
134 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.82425 (8)	0.32671 (8)	0.07136 (5)	0.0212 (2)
S2	0.7731 (2)	0.1352 (3)	0.61560 (16)	0.0177 (3)	0.683 (3)
O1	0.0398 (3)	0.3931 (2)	0.34150 (16)	0.0214 (4)
N1	0.3814 (3)	0.3582 (3)	0.19518 (18)	0.0165 (4)
H1	0.3243	0.3831	0.1247	0.020*
N2	0.6346 (3)	0.2730 (3)	0.32364 (17)	0.0155 (4)
H2	0.7665	0.2340	0.3513	0.019*
C1	0.6123 (4)	0.3176 (3)	0.1982 (2)	0.0161 (4)
C2	0.2501 (4)	0.3552 (3)	0.3155 (2)	0.0165 (5)
C3	0.4173 (3)	0.2981 (3)	0.4032 (2)	0.0153 (4)
C4	0.3529 (4)	0.2791 (3)	0.5309 (2)	0.0172 (5)
H4	0.1912	0.3066	0.5592	0.021*
C5	0.484 (2)	0.225 (8)	0.6318 (12)	0.017 (2)	0.683 (3)
C6	0.388 (2)	0.234 (2)	0.7571 (9)	0.0201 (7)	0.683 (3)
H6	0.2288	0.2766	0.7856	0.024*	0.683 (3)
C7	0.5563 (7)	0.1717 (7)	0.8394 (5)	0.0218 (9)	0.683 (3)
H7	0.5228	0.1714	0.9280	0.026*	0.683 (3)
C8	0.7709 (9)	0.1127 (9)	0.7737 (4)	0.0227 (12)	0.683 (3)
H8	0.9045	0.0645	0.8122	0.027*	0.683 (3)
S2'	0.3819 (11)	0.2103 (10)	0.7847 (4)	0.0201 (7)	0.317
C5'	0.494 (4)	0.210 (17)	0.628 (2)	0.017 (2)	0.317
C6'	0.731 (3)	0.159 (3)	0.6117 (17)	0.0177 (3)	0.317
H6'	0.8277	0.1592	0.5304	0.021*	0.317 (3)
C7'	0.816 (3)	0.106 (2)	0.7307 (10)	0.0227 (12)	0.317
H7'	0.9731	0.0609	0.7379	0.027*	0.317 (3)
C8'	0.6415 (17)	0.1274 (17)	0.8312 (14)	0.0218 (9)	0.317
H8'	0.6628	0.0994	0.9177	0.026*	0.317 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0143 (3)	0.0310 (3)	0.0138 (3)	−0.0020 (2)	−0.0009 (2)	−0.0024 (2)
S2	0.0127 (7)	0.0198 (7)	0.0184 (5)	−0.0001 (5)	−0.0058 (5)	−0.0018 (4)
O1	0.0122 (7)	0.0315 (9)	0.0211 (9)	−0.0048 (6)	−0.0035 (6)	−0.0068 (7)
N1	0.0139 (8)	0.0223 (9)	0.0131 (9)	−0.0046 (7)	−0.0041 (7)	−0.0020 (7)
N2	0.0108 (8)	0.0213 (9)	0.0129 (9)	−0.0026 (6)	−0.0037 (7)	−0.0013 (7)
C1	0.0149 (10)	0.0173 (9)	0.0154 (11)	−0.0047 (7)	−0.0035 (8)	−0.0012 (8)
C2	0.0159 (10)	0.0186 (10)	0.0157 (11)	−0.0062 (8)	−0.0021 (8)	−0.0035 (8)
C3	0.0137 (10)	0.0162 (9)	0.0153 (11)	−0.0041 (7)	−0.0034 (8)	−0.0014 (8)
C4	0.0155 (10)	0.0182 (10)	0.0180 (11)	−0.0057 (8)	−0.0026 (8)	−0.0034 (8)
C5	0.0229 (15)	0.014 (7)	0.0159 (13)	−0.007 (2)	−0.0053 (11)	−0.0011 (14)
C6	0.0226 (7)	0.0262 (17)	0.011 (2)	−0.0063 (8)	−0.0009 (15)	−0.0042 (16)
C7	0.034 (3)	0.020 (2)	0.0125 (14)	−0.0076 (19)	−0.004 (2)	−0.0041 (14)
C8	0.031 (4)	0.0192 (13)	0.018 (3)	−0.0072 (17)	−0.012 (3)	0.003 (2)
S2'	0.0226 (7)	0.0262 (17)	0.011 (2)	−0.0063 (8)	−0.0009 (15)	−0.0042 (16)
C5'	0.0229 (15)	0.014 (7)	0.0159 (13)	−0.007 (2)	−0.0053 (11)	−0.0011 (14)
C6'	0.0127 (7)	0.0198 (7)	0.0184 (5)	−0.0001 (5)	−0.0058 (5)	−0.0018 (4)
C7'	0.031 (4)	0.0192 (13)	0.018 (3)	−0.0072 (17)	−0.012 (3)	0.003 (2)
C8'	0.034 (3)	0.020 (2)	0.0125 (14)	−0.0076 (19)	−0.004 (2)	−0.0041 (14)

Geometric parameters (Å, º) top

S1—C1	1.660 (2)	C5—C6	1.380 (13)
S2—C5	1.706 (9)	C6—C7	1.433 (13)
S2—C8	1.702 (5)	C6—H6	0.9500
O1—C2	1.224 (3)	C7—C8	1.368 (5)
N1—C1	1.373 (3)	C7—H7	0.9500
N1—C2	1.374 (3)	C8—H8	0.9500
N1—H1	0.8800	S2'—C8'	1.693 (9)
N2—C1	1.358 (3)	S2'—C5'	1.705 (17)
N2—C3	1.407 (3)	C5'—C6'	1.378 (16)
N2—H2	0.8800	C6'—C7'	1.438 (15)
C2—C3	1.476 (3)	C6'—H6'	0.9500
C3—C4	1.344 (3)	C7'—C8'	1.356 (9)
C4—C5'	1.430 (8)	C7'—H7'	0.9500
C4—C5	1.431 (5)	C8'—H8'	0.9500
C4—H4	0.9500

C5—S2—C8	92.3 (3)	C4—C5—S2	125.2 (7)
C1—N1—C2	111.81 (19)	C5—C6—C7	112.6 (10)
C1—N1—H1	124.1	C5—C6—H6	123.7
C2—N1—H1	124.1	C7—C6—H6	123.7
C1—N2—C3	110.50 (17)	C8—C7—C6	111.1 (7)
C1—N2—H2	124.8	C8—C7—H7	124.4
C3—N2—H2	124.8	C6—C7—H7	124.4
N2—C1—N1	107.33 (18)	C7—C8—S2	112.7 (5)
N2—C1—S1	126.45 (16)	C7—C8—H8	123.6
N1—C1—S1	126.20 (17)	S2—C8—H8	123.6
O1—C2—N1	126.4 (2)	C8'—S2'—C5'	93.5 (8)
O1—C2—C3	128.6 (2)	C6'—C5'—C4	128.4 (16)
N1—C2—C3	104.99 (17)	C6'—C5'—S2'	109.6 (10)
C4—C3—N2	132.2 (2)	C4—C5'—S2'	121.5 (14)
C4—C3—C2	122.56 (19)	C5'—C6'—C7'	113.2 (14)
N2—C3—C2	105.19 (18)	C5'—C6'—H6'	123.4
C3—C4—C5'	128.4 (9)	C7'—C6'—H6'	123.4
C3—C4—C5	131.6 (5)	C8'—C7'—C6'	111.3 (16)
C3—C4—H4	114.2	C8'—C7'—H7'	124.4
C5'—C4—H4	117.3	C6'—C7'—H7'	124.4
C5—C4—H4	114.2	C7'—C8'—S2'	112.2 (13)
C6—C5—C4	123.6 (9)	C7'—C8'—H8'	123.9
C6—C5—S2	111.2 (6)	S2'—C8'—H8'	123.9

C3—N2—C1—N1	−4.2 (2)	O1—C2—C3—C4	0.3 (3)
C3—N2—C1—S1	174.52 (16)	N1—C2—C3—C4	−179.96 (19)
C2—N1—C1—N2	4.3 (2)	O1—C2—C3—N2	−179.7 (2)
C2—N1—C1—S1	−174.39 (16)	N1—C2—C3—N2	0.1 (2)
C1—N1—C2—O1	177.1 (2)	C6—C7—C8—S2	1.0 (8)
C1—N1—C2—C3	−2.7 (2)	C5—S2—C8—C7	0.0 (18)
C1—N2—C3—C4	−177.4 (2)	C6'—C7'—C8'—S2'	−0.1 (18)
C1—N2—C3—C2	2.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.88	2.20	2.873 (2)	133

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₈H₆N₂OS₂
M_r	210.27
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.1022 (6), 7.0806 (8), 11.0425 (13)
α, β, γ (°)	72.582 (11), 76.116 (10), 75.640 (9)
V (Å³)	433.87 (8)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	5.22
Crystal size (mm)	0.25 × 0.20 × 0.02

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.356, 0.903
No. of measured, independent and observed [I > 2σ(I)] reflections	2599, 1677, 1519
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.122, 1.04
No. of reflections	1677
No. of parameters	134
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.44

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.88	2.20	2.873 (2)	133

Symmetry code: (i) x+1, y, z.

Acknowledgements

We thank King Abdulaziz University and the University of Malaya for supporting this study.

References

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